Fungicidal active substance combinations

ABSTRACT

The invention relates to novel active substance combinations of valinamide derivatives of formula (I), wherein R 1  and R 2  have the meaning cited in the description, and fenamidone. The invention also relates to the use of novel active substance combinations to combat phytopathogenic fungi.

This application is a 371 of PCT/EP00/00505, filed Jan. 24, 2000.

The present application relates to novel active compound combinationscomprising on the one hand valinamide derivatives and on the other handfenamidone and which are highly suitable for controlling phytopathogenicfungi.

It is already known that valinamide derivatives have fungicidalproperties (cf. EP-A 472 996). The activity of this substance is good;however at low application rates it is sometimes unsatisfactory.

Furthermore, it is already known that fenamidone can be employed forcontrolling fungi (cf. EP-A 0 629 616). However, the activity offenamidone at low application rates is not always satisfactory.

It has now been found that the novel active compound combinations ofvalinamide derivatives of the general formula (I)

in which

R¹ represents i-propyl or s-butyl and

R² represents chlorine, methyl, ethyl or methoxy, and

fenamidone of the formula (II)

have very good fungicidal properties.

Surprisingly, the fungicidal activity of the active compoundcombinations according to the invention is considerably higher than thesum of the activities of the individual active compounds. This is anunforeseeable true synergistic effect and not just a complementation ofaction.

From the structural formula for the active compounds of the formula (I)it can be seen that the compounds have two asymmetrically substitutedcarbon atoms. The product can therefore be present as a mixture ofvarious isomers or else in the form of an individual isomer.

Preferred compounds of the formula (I) are compounds in which the aminoacid moiety is formed by i-propyloxycarbonyl-L-valine orsec-butyloxycarbonyl-L-valine and the phenethylamine moiety is eitherracemic or has the S-(−)-configuration, but in particular theR-(+)-configuration.

Particularly preferred compounds of the formula (I) are the compounds inwhich

R¹ represents i-propyl.

In particular, the compounds

1-methylethyl[2-methyl-1-[[[-1-(4-chlorophenyl)ethyl]amino]carbonyl]-propyl]-carbamateof the formula (Ia)

1-methylethyl[2-methyl-1-[[[-1-(4-methylphenyl)ethyl]amino]carbonyl]-propyl]-carbamateof the formula (Ib)

1-methylethyl[2-methyl-1-[[[-1-(4-ethylphenyl)ethyl]amino]carbonyl]-propyl]-carbamateof the formula (Ic)

and 1-methylethyl[2-methyl-1-[[[-1-(4-methoxyphenyl)ethyl]amino]carbonyl]-propyl]-carbamateof the formula (Id)

and their isomers, as mentioned above, may be mentioned.

The active compounds of the formula (I) are known (cf. EP-A-0 472 996).

The fungicidally active compound fenamidone, which is furthermorepresent in the combinations according to the invention, is also known(cf. EP-A 0 629 616).

In addition to at least one active compound of the formula (I), theactive compound combinations according to the invention comprise theactive compound fenamidone of the formula (II). They may additionallyalso comprise other fungicidally active admixture components.

If the active compounds in the active compound combinations according tothe invention are present in certain ratios by weight, the synergisticeffect is particularly pronounced. However, the ratios by weight of theactive compounds in the active compound combinations can be variedwithin a relatively wide range. In general,

from 0.1 to 10 parts by weight, preferably

from 0.2 to 2 parts by weight of active compound of the formula (II)

are present per part by weight of active compound of the formula (I).

The active compound combinations according to the invention have verygood fungicidal properties and can be employed in particular forcontrolling phytopathogenic fungi, such as Plasmodiophoromycetes,Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,Deuteromycetes, etc.

The active compound combinations according to the invention areparticularly suitable for the protective control of Phytophthorainfestans and Alternaria spec. on tomatoes and potatoes, and ofPlasopara viticola on grapevines.

The fact that the active compound combinations are well tolerated byplants at the concentrations required for controlling plant diseasespermits the treatment of above-ground parts of plants, of propagationstock and seeds, and of the soil.

The active compound combinations according to the invention can beconverted into the customary formulations, such as solutions, emulsions,suspensions, powders, foams, pastes, granules, aerosols andmicroencapsulations in polymeric substances and in coating compositionsfor seeds, and ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds or active compound combinations with extenders,that is liquid solvents, liquefied gases under pressure, and/or solidcarriers, optionally with the use of surfactants, that is emulsifiersand/or dispersants, and/or foam formers. If the extender used is water,it is also possible to use, for example, organic solvents as auxiliarysolvents. Essentially, suitable liquid solvents include: aromatics suchas xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water. Liquefied gaseous extenders or carriers areto be understood as meaning liquids which are gaseous at ambienttemperature and under atmospheric pressure, for example aerosolpropellants such as butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as finely dividedsilica, alumina and silicates. Suitable solid carriers for granules are:for example crushed and fractionated natural rocks such as calcite,marble, pumice, sepiolite and dolomite, or else synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks. Suitableemulsifiers and/or foam formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates, or else proteinhydrolysates. Suitable dispersants are: for example lignin-sulphitewaste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

In the formulations, the active compound combinations according to theinvention can be present as a mixture with other active compounds suchas fungicides, insecticides, acaricides and herbicides, and as mixtureswith fertilizers or plant growth regulators.

Mixing partners for such mixtures are, for example:

Fungicides

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]-acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulphide, captafol, captan, carbendazim, carboxin, quinomethionate,chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol,diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole,dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine,dipyrithion, ditalimfos, dithianon, dodine, drazoxolon, edifenphos,epoxyconazole, ethirimol, etridiazole, fenarimnol, fenbuconazole,fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil,fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fthalide, fuberidazole,furalaxyl, funnecyclox, guazatine, hexachlorobenzene, hexaconazole,hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),iprodione, isoprothiolane, kasugamycin, copper preparations such as:copper hydroxide, copper naphthenate, copper oxychloride, coppersulphate, copper oxide, oxine-copper and Bordeaux mixture, mancopper,mancozcb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole,methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz,procymidone, propamocarb, propiconazole, propineb, pyrazophos,pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB), sulphur andsulphur preparations, tebucanozole, tecloftalam, tecnazene,tetraconazole, thiabendazole, thicyofen, thiophanate-methyl, thiram,tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide,trichlamide, tricyclazole, tridemorph, triflumizole, triforin,triticonazole, validamycin A, vinclozolin, zineb, ziram.

Bactericides

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avernectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb,benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben,cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chloretoxyfos,chlorfenvinphos, chlorfluazuron, chlomiephos, chlorpyrifos, chlorpyrifosM, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,deltamethlrin, demneton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, diclilorvos, dicliphos, -dicrotophos,diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion,disulfoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,ethofenprox, ethoprophos, etofenprox, etrimphos, fenamiphos, fenazaquin,fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb,fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil,fluazinam, flucycloxuron, flucythirinate, flufenoxuron, flufenprox,fluvalinate, fonophos, formothion, fosthiazate, fubfenprox,furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid,iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivemectin,lamda-cyhalothlrin, lufenuron, malathion, mecarbam, mervinphos,mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion,methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M,oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamdon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenofos, profenophos, promecarb, propaphos, propoxur,prothiofos, prothiophos, prothoate, pymetrozin, pyrachlophos,pyraclofos, pyraclophos, pyradaphenthion, pyresmethrin, pyrethrum;,pyridaben, pyrimidifen, pyriproxifen, quinalphos, RH 5992, salithion,sebufos, silafluofen, sulfotep, sulprofos, tebufenozid, tebufenpyrad,tebupirimphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos,tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon,thionazin, thuringiensin, tralomethrin, triarathen, triazophos,triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC,xylylcarb, YI 5301/5302, zetamethrin.

The active compound combinations can be used as such, in the form oftheir formulations or as the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, wettable powders, soluble powders and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, spreading, and as a powder for dry seedtreatment, a solution for seed treatment, a water-soluble powder forseed treatment, a water-soluble powder for slurry treatment, or byencrusting.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a relatively wide range. Ingeneral, they are between 1 and 0.0001% by weight, preferably between0.5 and 0.001%.

In the treatment of the seeds, amounts of active compound of generallyfrom 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 10 g,are required.

In the treatment of the soil, active compound concentrations of from0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% by weight,are required at the site of action.

The good fungicidal activity of the active compound combinationsaccording to the invention is evident from the examples below. While theindividual active compounds exhibit weaknesses with regard to thefungicidal activity, the combinations have an activity which exceeds asimple addition of activities.

A synergistic effect of fungicides is always present when the fungicidalactivity of the active compound combinations exceeds the total of theactivities of the active compounds when applied individually.

The expected activity for a given combination of two active compoundscan be calculated as follows (cf. Colby, S.R., “Calculating Synergisticand Antagonistic Responses of Herbicide Combinations”, Weeds 15, pages20-22, 1967):

X is the efficacy, expressed in % of the untreated control, whenapplying the active compound A at a concentration of m g/ha,

Y is the efficacy, expressed in % of the untreated control, whenapplying the active compound B at a concentration of n g/ha,

E is the expected efficacy, expressed in % of the untreated control,when applying the active compound A and B at a concentration of m and ng/ha, ${{then}{\quad \quad}E} = {X + Y - {\frac{X \cdot N}{100}.}}$

If the actual fungicidal activity exceeds the calculated value, then theactivity of the combination is superadditive, i.e. a synergistic effectexists. In this case, the efficacy which was actually observed must begreater than the value for the expected efficacy (E) calculated from theabovementioned formula.

EXAMPLE Plasmopara Test (Grapevine)/Protective

To produce a suitable preparation of active compound, either commercialactive compound formulations (individual active compounds or activecompound combinations) or 1 part by weight of active compound are mixedwith 4.7 parts by weight of solvent (acetone) and 0.3 parts by weight ofemulsifier (alkyl-aryl polyglycol ether), and the mixture is dilutedwith water to the particular desired concentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain in an incubationcabin at approximately 20° C. and 100% relative atmospheric humidity for1 day. The plants are subsequently placed in a greenhouse atapproximately 21° C. and approximately 90% relative atmospheric humidityfor 5 days. The plants are then moistened and placed in an incubationcabin for 1 day.

Evaluation is carried out 6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

The observed activity of the active compound combination according tothe invention is greater than the calculated activity, i.e. asynergistic effect is present. At a mixing ratio of 1:1 and anapplication rate of 5 g/ha, the combination iprovalicarb and fenamidonehas an actual efficacy of 98%. The expected value calculated usingColby's formula is, at 45%, considerably lower.

What is claimed is:
 1. An active compound combination, comprising asynergistic fungicidally effective combination of: a) a first activecompound comprising at least one valinamide derivative of the Formula(I)

 in which R¹ represents i-propyl or s-butyl and R² represents chlorine,methyl, ethyl or methoxy; and a second active compound comprising afenamidone of Formula (II)

wherein the weight ratio of said first active compound of the Formula(I) to said second active compound of the Formula (II) is from 1:0.1 to1:10.
 2. A fungicidal composition comprising an active compoundcombination as defined in claim 1 and one or more agents selected fromthe group consisting of extenders and surfactants, wherein the weightratio of said active compound of the Formula (I) to said active compoundof the Formula (II) in said fungicidal composition is from 1:0.1 to1:10.
 3. An active compound combination, comprising a synergisticfungicidally effective combination of: a) a first active compoundcomprising at least one valinamide derivative of the Formula (I)

 in which R¹ represents i-propyl or s-butyl and R² represents chlorine,methyl, ethyl or methoxy; and a second active compound comprising afenamidone of Formula (II)


4. An active compound combination according to claim 1 wherein theweight ratio of said first active compound of the Formula (I) to saidsecond active compound of the Formula (II) is from 1:0.2 to 1:2.
 5. Amethod for controlling fungi, comprising the step of applying afungicidally effective amount of an active compound combination asdefined in claim 1 to a member selected from the group consisting ofsaid fungi, a habitat of said fungi and combinations thereof.
 6. Aprocess for preparing a fungicidal composition, comprising the step ofmixing an active compound combination according to claim 1 with one ormore agents selected from the group consisting of extenders andsurfactants.